TW201418396A - Adhesive composition and film-shaped adhesive - Google Patents
Adhesive composition and film-shaped adhesive Download PDFInfo
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- TW201418396A TW201418396A TW102136809A TW102136809A TW201418396A TW 201418396 A TW201418396 A TW 201418396A TW 102136809 A TW102136809 A TW 102136809A TW 102136809 A TW102136809 A TW 102136809A TW 201418396 A TW201418396 A TW 201418396A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本發明是有關於一種黏著劑組成物以及膜狀黏著劑。 This invention relates to an adhesive composition and a film adhesive.
醯胺系黏著樹脂兼具對例如250℃的溫度的耐熱性與黏著性,因此可用作應對高溫製程(process)的黏著劑(例如參照專利文獻1)。 Since the amide-based adhesive resin has heat resistance and adhesion to, for example, a temperature of 250 ° C, it can be used as an adhesive for a high-temperature process (see, for example, Patent Document 1).
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]國際公開第2012/140740號 [Patent Document 1] International Publication No. 2012/140740
且說,在欲將黏著劑用於電子材料的製造步驟的情況下,理想的是具備不溶解於步驟中所使用的抗蝕劑(resist)、抗蝕劑剝離液等中所使用的有機溶劑的性能、即耐化學品性。然而,先前的醯胺系黏著樹脂溶解於上述用途中通常所使用的有機溶劑(例如,N-甲基吡咯啶酮、四氫呋喃等),因此使用方面存在限制。 In the case where the adhesive is to be used in the production step of an electronic material, it is preferable to provide an organic solvent which is not dissolved in a resist, a resist stripper, or the like used in the step. Performance, ie chemical resistance. However, the prior guanamine-based adhesive resin is dissolved in an organic solvent (for example, N-methylpyrrolidone, tetrahydrofuran, etc.) which is usually used in the above-mentioned use, and thus there is a limitation in use.
因此,本發明的目的在於提供一種耐化學品性優異的含有聚醯胺樹脂的黏著劑組成物以及使用該組成物的膜狀黏著劑。 Accordingly, an object of the present invention is to provide an adhesive composition containing a polyamide resin excellent in chemical resistance and a film adhesive using the same.
本發明提供一種含有環氧樹脂以及聚醯胺樹脂的黏著劑組成物。此種黏著劑組成物的耐熱性以及耐化學品性優異。本發明的黏著劑組成物尤其可尤佳地用作在200℃~270℃的溫度範圍內所使用的黏著劑。 The present invention provides an adhesive composition comprising an epoxy resin and a polyamide resin. Such an adhesive composition is excellent in heat resistance and chemical resistance. The adhesive composition of the present invention is particularly preferably used as an adhesive used in a temperature range of from 200 ° C to 270 ° C.
聚醯胺樹脂較佳為具有聚氧烷二基(polyoxyalkanediyl group)。藉由聚氧烷二基而使黏著劑組成物的柔軟性以及黏著性變得良好。 The polyamide resin preferably has a polyoxyalkanediyl group. The flexibility and adhesion of the adhesive composition are improved by the polyoxyalkylene group.
聚醯胺樹脂較佳為具有二價芳香環基。藉由二價芳香環基的存在而使黏著劑組成物在高溫下的黏著性變得更良好。 The polyamide resin preferably has a divalent aromatic ring group. The adhesion of the adhesive composition at a high temperature is further improved by the presence of a divalent aromatic ring group.
聚醯胺樹脂較佳為具有羥基。藉此,黏著劑組成物的耐化學品性變得更良好。 The polyamide resin preferably has a hydroxyl group. Thereby, the chemical resistance of the adhesive composition becomes better.
聚醯胺樹脂亦可具有1,4-哌嗪二基(1,4-piperazinediyl group)。 The polyamide resin may also have a 1,4-piperazinediyl group.
此外,黏著劑組成物亦可以形成為膜狀而成的膜狀黏著劑的形式提供。 Further, the adhesive composition may be provided in the form of a film-like adhesive which is formed into a film.
根據本發明,可提供一種耐化學品性優異的含有聚醯胺樹脂的黏著劑組成物以及使用該組成物的膜狀黏著劑。 According to the present invention, it is possible to provide an adhesive composition containing a polyamide resin excellent in chemical resistance and a film adhesive using the same.
本實施方式的黏著劑組成物含有聚醯胺樹脂以及環氧 樹脂。此外,本發明中,所謂「黏著性」,是指在20℃~22℃的溫度下以10弧度(radian)/秒測定的儲存彈性模數(G')小於3×105帕斯卡(pascal)(達爾奎斯特(Dahlquist)基準)。 The adhesive composition of the present embodiment contains a polyamide resin and an epoxy resin. Further, in the present invention, the term "adhesiveness" means that the storage elastic modulus (G') measured at 10 radians/second at a temperature of 20 ° C to 22 ° C is less than 3 × 10 5 Pascal. (Dahlquist benchmark).
(聚醯胺樹脂) (polyamide resin)
聚醯胺樹脂在主鏈上具有醯胺基,且主鏈的末端具有胺基、羧基、羧酸鹵化物結構或羧酸酐結構。主鏈的末端亦可為源自下述改質中所使用的化合物的基團。此外,羧酸鹵化物結構例如可列舉如-COCl、-COBr的醯鹵基,所謂羧酸酐結構,意指由多個羧基生成的酸酐基。 The polyamide resin has a mercaptoamine group in the main chain, and the terminal of the main chain has an amine group, a carboxyl group, a carboxylic acid halide structure or a carboxylic anhydride structure. The end of the main chain may also be a group derived from a compound used in the modification described below. Further, examples of the carboxylic acid halide structure include a hydrazine halide group such as -COCl and -COBr, and a carboxylic acid anhydride structure means an acid anhydride group formed of a plurality of carboxyl groups.
聚醯胺樹脂較佳為具有下述式(1-1)所表示的結構單元。 The polyamide resin preferably has a structural unit represented by the following formula (1-1).
上述式(1-1)中,R1以及R2表示二價有機基。R1較佳為自選自由鏈式脂肪族化合物、環式脂肪族化合物(包含脂環式化合物、交聯環式化合物、螺環烴)、具有苯環的化合物(包含萘、蒽、稠四苯、芘、苝等縮合多環式烴以及苯)以及雜環式化合物所組成的組群中的化合物中去除兩個氫原子所得的二價有機基。 In the above formula (1-1), R 1 and R 2 represent a divalent organic group. R 1 is preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound, a crosslinked cyclic compound, a spirocyclic hydrocarbon), a compound having a benzene ring (including naphthalene, anthracene, and fused tetraphenyl). a divalent organic group obtained by removing two hydrogen atoms from a compound in a group consisting of condensed polycyclic hydrocarbons such as hydrazine and hydrazine and benzene) and a heterocyclic compound.
R2較佳為自選自由鏈式脂肪族化合物、環式脂肪族化合物(包含具備亞甲基二環己基的化合物等脂環式化合物、交聯環 式化合物、螺環烴)、具有苯環的化合物(包含萘、蒽、稠四苯、芘、苝等縮合多環式烴以及苯)、雜環式化合物、聚環氧烷(包含聚環氧乙烷、聚環氧丙烷)以及聚有機矽氧烷(包含聚二甲基矽氧烷、聚甲基苯基矽氧烷)所組成的組群中的化合物或其鹵化物(氟化物等)中去除兩個氫原子所得的二價有機基。此外,上文作為提供R2的化合物所述的具有苯環的化合物中包含2,2-雙(4-苯氧基苯基)丙烷、2,2-雙(4-苯氧基苯基)碸、2,2-雙(4-苯氧基苯基)甲烷、4,4'-雙苯氧基聯苯、雙(4-苯氧基苯基)醚、雙(4-苯氧基苯基)酮、1,3-苯氧基苯、1,4-苯氧基苯、2,2'-二甲基聯苯、5,5'-二甲基-2,2'-磺醯基-聯苯、二苯醚、二苯基碸、二苯甲酮、二苯基甲烷等。 R 2 is preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound such as a compound having a methylene dicyclohexyl group, a crosslinked cyclic compound, a spirocyclic hydrocarbon), and a benzene ring. Compounds (including condensed polycyclic hydrocarbons such as naphthalene, anthracene, fused tetraphenyl, anthracene, fluorene, and benzene), heterocyclic compounds, polyalkylene oxides (including polyethylene oxide, polypropylene oxide), and polyorganoindenes a divalent organic group obtained by removing two hydrogen atoms from a compound or a halide thereof (fluoride or the like) of a group consisting of oxyalkylene (including polydimethyl siloxane or polymethylphenyl siloxane) . Further, the compound having a benzene ring as described above for the compound providing R 2 contains 2,2-bis(4-phenoxyphenyl)propane and 2,2-bis(4-phenoxyphenyl). Bismuth, 2,2-bis(4-phenoxyphenyl)methane, 4,4'-bisphenoxybiphenyl, bis(4-phenoxyphenyl)ether, bis(4-phenoxybenzene) Ketone, 1,3-phenoxybenzene, 1,4-phenoxybenzene, 2,2'-dimethylbiphenyl, 5,5'-dimethyl-2,2'-sulfonyl -biphenyl, diphenyl ether, diphenyl hydrazine, benzophenone, diphenylmethane, and the like.
聚醯胺樹脂較佳為具有聚氧烷二基。藉由使聚醯胺樹脂含有聚氧烷二基,而使黏著劑組成物的玻璃轉移溫度(glass transition temperature)降低,例如在室溫等低溫下變得容易黏附,黏著性變得優異。聚氧烷二基可列舉下述式(2)所表示的基團。式中,n表示2以上的整數,R6表示烷二基。此處,所存在的多個R6可相互相同亦可不同。 The polyamide resin preferably has a polyoxyalkylene group. When the polyamide resin contains a polyoxyalkylene group, the glass transition temperature of the adhesive composition is lowered, for example, it becomes easy to adhere at a low temperature such as room temperature, and the adhesiveness is excellent. The polyoxyalkylene group may be a group represented by the following formula (2). In the formula, n represents an integer of 2 or more, and R 6 represents an alkanediyl group. Here, the plurality of R 6 may be present in the same or different from each other.
上述式(2)中,R6可為直鏈狀亦可為分支狀,較佳為碳數2~4的烷二基,更佳為碳數2~3的烷二基。R6例如可列舉: 乙烷-1,2-二基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基。n較佳為2~70,更佳為6~33。 In the above formula (2), R 6 may be linear or branched, preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 3 carbon atoms. Examples of R 6 include an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group. n is preferably 2 to 70, more preferably 6 to 33.
聚氧烷二基較佳為由聚環氧乙烷、聚環氧丙烷、聚環氧丁烷、聚氧化四亚甲基醚(polytetramethylene oxide)、聚環氧乙烷-聚環氧丙烷共聚物、聚乙二醇-聚醚雙醇(polytetramethylene glycol)共聚物、聚丙二醇-聚醚雙醇共聚物、聚乙二醇-聚丙二醇-聚醚雙醇共聚物等聚環氧烷衍生的基團,更佳為聚氧乙烯基、聚氧丙烷-1,2-二基。 The polyoxyalkylene di-group is preferably composed of polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer. Polyalkylene oxide-derived groups such as polyethylene glycol-polytetramethylene glycol copolymer, polypropylene glycol-polyether diol copolymer, polyethylene glycol-polypropylene glycol-polyether diol copolymer More preferably, it is a polyoxyethylene group or a polyoxypropylene-1,2-diyl group.
將聚氧烷二基導入至聚醯胺樹脂的方法簡便的是使用至少一種原料(聚合性單體)中具有聚氧烷二基的原料。 The method of introducing the polyoxyalkylene diamine into the polyamine resin is simply a use of a raw material having a polyoxyalkylene group in at least one raw material (polymerizable monomer).
聚醯胺樹脂例如可藉由下述式(A-1)所表示的單體(A-1)與下述式(B-1)所表示的單體(B-1)的縮合聚合而獲得。可使單體(A-1)的羧基轉化為醯氯基而形成聚醯胺,亦可利用其他方法製造。單體(A-1)以及單體(B-1)可分別單獨使用一種,亦可組合使用兩種以上。此外,下述式(A-1)以及式(B-1)中的R1以及R2的定義以及較佳例如上所述。 The polyamine resin can be obtained, for example, by condensation polymerization of the monomer (A-1) represented by the following formula (A-1) and the monomer (B-1) represented by the following formula (B-1). . The carboxyl group of the monomer (A-1) can be converted into a fluorenyl chloride group to form a polydecylamine, which can also be produced by other methods. The monomer (A-1) and the monomer (B-1) may be used alone or in combination of two or more. Further, the definitions of R 1 and R 2 in the following formula (A-1) and formula (B-1) are preferably as described above.
HOOC-R1-COOH (A-1) HOOC-R 1 -COOH (A-1)
H2N-R2-NH2 (B-1) H 2 NR 2 -NH 2 (B-1)
單體(A-1)可列舉:草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、1,9-壬烷二羧酸、十二烷二酸、十四烷二酸、十五烷二酸、十八烷二酸等伸烷基二羧酸,鄰苯二甲酸、對苯二甲酸、間苯二甲酸、1,4-萘二羧酸、1,5-萘二羧酸、2,6-萘二羧酸等伸芳基二羧酸,4-甲基六氫鄰苯二甲酸、3-甲基六氫鄰苯二甲酸、2-甲基六氫鄰苯二甲酸、3-乙基六氫鄰苯二甲酸、2-乙基六氫鄰苯二甲酸、甲基降莰烷-2,3-二羧酸、甲基降莰烷-3,4-二羧酸等具有環己烷骨架的二羧酸等。就黏著劑組成物的耐熱性提高而言,較佳為伸芳基二羧酸。 Examples of the monomer (A-1) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and 1,9-decane. Dicarboxylic acid, dodecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, etc. alkyl dicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, Aryl dicarboxylic acid such as 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4-methylhexahydrophthalic acid, 3-methyl six Hydrogen phthalic acid, 2-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 2-ethylhexahydrophthalic acid, methylnorbornane-2,3-di A dicarboxylic acid having a cyclohexane skeleton such as a carboxylic acid or methylnorbornane-3,4-dicarboxylic acid. In terms of improvement in heat resistance of the adhesive composition, an aryldicarboxylic acid is preferred.
單體(B-1)可列舉:2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、雙[4-(4-胺基苯氧基)苯基]甲烷、4,4'-雙(4-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)苯基]酮、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、2,2'-二甲基聯苯-4,4'-二胺、2,2'-雙(三氟甲基)聯苯-4,4'-二胺、5,5'-二甲基-2,2'-磺醯基-聯苯-4,4'-二胺、(4,4'-二胺基)二苯醚、(4,4'-二胺基)二苯基碸、(4,4'-二胺基)二苯甲酮、(3,3'-二胺基)二苯甲酮、(4,4'-二胺基)二苯基甲烷、(4,4'-二胺基)二苯醚、(3,3'-二胺基)二苯醚、N,N'-雙(4-胺基苯基)哌嗪等芳香族二胺,伸乙基二胺、伸丙基二胺等伸烷基二胺,聚環氧乙烷二胺、聚環氧 丙烷二胺等聚環氧烷二胺,(4,4'-二胺基)二環己基甲烷、異佛酮二胺、1,4-雙胺基丙基哌嗪、[3,4-雙(1-胺基庚基)-6-己基-5-(1-辛烯基)]環己烯、雙胺基甲基降莰烯等脂肪族二胺,聚二甲基矽氧烷二胺等矽氧烷二胺等。 The monomer (B-1) may, for example, be 2,2-bis[4-(4-aminophenoxy)phenyl]propane or bis[4-(3-aminophenoxy)phenyl]anthracene. Bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-(4-amine Phenoxy)phenyl]methane, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4- (4-Aminophenoxy)phenyl]one, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2' - dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 5,5'-dimethyl-2,2 '-sulfonyl-biphenyl-4,4'-diamine, (4,4'-diamino)diphenyl ether, (4,4'-diamino)diphenylanthracene, (4,4 '-Diamino)benzophenone, (3,3'-diamino)benzophenone, (4,4'-diamino)diphenylmethane, (4,4'-diamino An aromatic diamine such as diphenyl ether, (3,3'-diamino)diphenyl ether or N,N'-bis(4-aminophenyl)piperazine, ethylidene diamine, and propyl group Diamines such as alkyl diamines, polyethylene oxide diamines, polyepoxys Polyalkylene oxide diamine such as propane diamine, (4,4'-diamino)dicyclohexylmethane, isophorone diamine, 1,4-diaminopropylpiperazine, [3,4-double Aliphatic diamines such as (1-aminoheptyl)-6-hexyl-5-(1-octenyl)]cyclohexene, dimethylaminomethylnordecene, polydimethyloxane diamine Isooxane diamine and the like.
聚醯胺樹脂較佳為具有聚氧烷二基,更佳為於結構單元中的源自單體(B-1)的結構中存在聚氧烷二基。即,較佳為單體(A-1)以及單體(B-1)中的至少一種具有聚氧烷二基,更佳為單體(B-1)中的至少一種具有聚氧烷二基。 The polyamine resin preferably has a polyoxyalkylene group, and more preferably a polyoxyalkylene group is present in the structure derived from the monomer (B-1) in the structural unit. That is, it is preferred that at least one of the monomer (A-1) and the monomer (B-1) has a polyoxyalkylene group, and more preferably at least one of the monomers (B-1) has a polyoxyalkylene group. base.
因此,聚醯胺樹脂較佳為具有使包含具有聚氧烷二基以及至少兩個胺基的單體(單體(b-1))的聚合性單體縮合聚合而獲得的結構單元。 Therefore, the polyamide resin preferably has a structural unit obtained by condensation-polymerizing a polymerizable monomer containing a monomer having a polyoxyalkylene group and at least two amine groups (monomer (b-1)).
聚合性單體中的單體(b-1)的含量相對於單體(B-1)的總量,較佳為5mol%~20mol%,更佳為7mol%~15mol%,進而較佳為8mol%~10mol%。具有使此種聚合性單體縮合聚合而獲得的結構單元的黏著劑組成物存在與被黏接體的密接性更優異的傾向。 The content of the monomer (b-1) in the polymerizable monomer is preferably from 5 mol% to 20 mol%, more preferably from 7 mol% to 15 mol%, more preferably from 7 mol% to 15 mol%, based on the total amount of the monomers (B-1). 8 mol% to 10 mol%. The adhesive composition having a structural unit obtained by condensation polymerization of such a polymerizable monomer tends to be more excellent in adhesion to the adherend.
單體(b-1)可列舉聚環氧烷聚胺。聚環氧烷聚胺較佳為聚環氧烷二胺或聚環氧烷三胺,此種胺可較佳地使用JEFFAMINE D-230(亨斯邁(HUNTSMAN),商品名)、JEFFAMINE D-400(HUNTSMAN,商品名)、JEFFAMINE D-2000(HUNTSMAN,商品名)、JEFFAMINE D-4000(HUNTSMAN,商品名)等聚環氧丙烷二胺,JEFFAMINE ED-600(HUNTSMAN, 商品名)、JEFFAMINE ED-900(HUNTSMAN,商品名)等聚環氧丙烷與聚環氧乙烷的共聚物二胺,JEFFAMINE EDR-148(HUNTSMAN,商品名)、JEFFAMINE EDR-176(HUNTSMAN,商品名)等聚環氧乙烷二胺,JEFFAMINE T-403(HUNTSMAN,商品名)、JEFFAMINE T-3000(HUNTSMAN,商品名)、JEFFAMINE T-5000(HUNTSMAN,商品名)等聚胺(聚氧丙烯三酸甘油酯三胺)等。該些可單獨使用或組合使用兩種以上。 The monomer (b-1) is exemplified by a polyalkylene oxide polyamine. The polyalkylene oxide polyamine is preferably a polyalkylene oxide diamine or a polyalkylene oxide triamine, and such an amine can preferably be JEFFAMINE D-230 (HUNTSMAN, trade name), JEFFAMINE D- Polypropylene oxide diamine such as 400 (HUNTSMAN, trade name), JEFFAMINE D-2000 (HUNTSMAN, trade name), JEFFAMINE D-4000 (HUNTSMAN, trade name), JEFFAMINE ED-600 (HUNTSMAN, Copolymer diamine of polyethylene oxide and polyethylene oxide such as JEFFAMINE ED-900 (HUNTSMAN, trade name), JEFFAMINE EDR-148 (HUNTSMAN, trade name), JEFFAMINE EDR-176 (HUNTSMAN, commodity Polyamine (polyoxypropylene) such as polyethylene oxide diamine, JEFFAMINE T-403 (HUNTSMAN, trade name), JEFFAMINE T-3000 (HUNTSMAN, trade name), JEFFAMINE T-5000 (HUNTSMAN, trade name) Triglyceride triamine) and the like. These may be used alone or in combination of two or more.
另外,聚醯胺樹脂較佳為具有脂環式結構。具有此種結構的黏著劑組成物可抑制吸水性。脂環式結構可列舉:環己基、二環己基、亞甲基二環己基、異佛酮基、環己基二甲基。 Further, the polyamide resin preferably has an alicyclic structure. The adhesive composition having such a structure can suppress water absorption. The alicyclic structure may, for example, be a cyclohexyl group, a dicyclohexyl group, a methylene dicyclohexyl group, an isophorone group or a cyclohexyldimethyl group.
作為具有此種脂環式結構的單體,單體(A-1)可例示1,4-二羧基環己烷,單體(B-I)可例示雙(4-胺基環己基)甲烷、異佛酮二胺以及1,3-雙(胺基甲基)環己烷。該些可單獨使用或組合使用兩種以上。 As the monomer having such an alicyclic structure, the monomer (A-1) can be exemplified by 1,4-dicarboxycyclohexane, and the monomer (BI) can be exemplified by bis(4-aminocyclohexyl)methane or the like. Carbaryl diamine and 1,3-bis(aminomethyl)cyclohexane. These may be used alone or in combination of two or more.
另外,聚醯胺樹脂較佳為在結構單元中具有亞甲基二環己基,更佳為在結構單元中的源自單體(B-1)的結構中存在亞甲基二環己基。即,較佳為單體(A-1)以及單體(B-1)中的至少一種具有亞甲基二環己基,更佳為單體(B-1)中的至少一種具有亞甲基二環己基。 Further, the polyamide resin preferably has a methylene dicyclohexyl group in the structural unit, and more preferably a methylene dicyclohexyl group is present in the structure derived from the monomer (B-1) in the structural unit. That is, it is preferred that at least one of the monomer (A-1) and the monomer (B-1) has a methylene dicyclohexyl group, and more preferably at least one of the monomers (B-1) has a methylene group. Dicyclohexyl.
即,聚醯胺樹脂較佳為具有使包含具有亞甲基雙環己基以及至少兩個胺基的單體(單體(b-2))的聚合性單體縮合聚合而獲得的結構單元。 That is, the polyamide resin preferably has a structural unit obtained by condensation-polymerizing a polymerizable monomer containing a monomer having a methylene dicyclohexyl group and at least two amine groups (monomer (b-2)).
聚合性單體中的單體(b-2)的含量相對於單體(B-1)的總量,較佳為4mol%~28.5mol%,更佳為8mol%~28.5mol%,進而較佳為8mol%~20mol%。具有使此種聚合性單體縮合聚合而獲得的結構單元的黏著劑組成物可抑制吸水率而保存穩定性更優異。 The content of the monomer (b-2) in the polymerizable monomer is preferably from 4 mol% to 28.5 mol%, more preferably from 8 mol% to 28.5 mol%, based on the total amount of the monomer (B-1). Preferably, it is 8 mol% to 20 mol%. The adhesive composition having a structural unit obtained by condensation-polymerizing such a polymerizable monomer can suppress water absorption and is more excellent in storage stability.
單體(b-2)可較佳地使用雙(4-胺基環己基)甲烷。 As the monomer (b-2), bis(4-aminocyclohexyl)methane can be preferably used.
關於聚醯胺樹脂,結構單元中的源自單體(B-1)的結構較佳為具有哌嗪二基,更佳為具有哌嗪-N,N'-二丙基。 As the polyamine resin, the structure derived from the monomer (B-1) in the structural unit preferably has a piperazine diyl group, more preferably a piperazine-N,N'-dipropyl group.
即,聚醯胺樹脂較佳為具有使包含具有哌嗪-N,N'-二丙基以及至少兩個胺基的單體(單體(b-3))的聚合性單體縮合聚合而獲得的結構單元。 That is, the polyamine resin preferably has a condensation polymerization polymerization of a polymerizable monomer containing a monomer having a piperazine-N,N'-dipropyl group and at least two amine groups (monomer (b-3)). The structural unit obtained.
聚合性單體中的單體(b-3)的含量並無特別限制,可使應用單體(b-1)以及(b-2)後的剩餘量為最大量而使用。根據具有使此種聚合性單體縮合聚合而獲得的結構單元的聚醯胺樹脂,可獲得耐熱性與黏著性的平衡(balance)優異的黏著劑組成物。 The content of the monomer (b-3) in the polymerizable monomer is not particularly limited, and the remaining amount after the application of the monomers (b-1) and (b-2) can be used in the maximum amount. According to the polyamine resin having a structural unit obtained by condensation polymerization of such a polymerizable monomer, an adhesive composition having excellent balance between heat resistance and adhesion can be obtained.
單體(b-3)可較佳地使用1,4-雙(3-胺基丙基)哌嗪。 As the monomer (b-3), 1,4-bis(3-aminopropyl)piperazine can be preferably used.
聚醯胺樹脂較佳為具有羥基,更佳為具有酚性羥基。藉由使聚醯胺樹脂具有羥基,而使耐化學品性進一步提高。將羥基導入至聚醯胺樹脂的方法,較佳為使用至少一種聚合性單體中具有羥基的原料。具有羥基的原料例如可列舉羥基間苯二甲酸。 The polyamide resin preferably has a hydroxyl group, more preferably a phenolic hydroxyl group. The chemical resistance is further improved by making the polyamide resin have a hydroxyl group. In the method of introducing a hydroxyl group into a polyamide resin, it is preferred to use a raw material having a hydroxyl group among at least one polymerizable monomer. Examples of the raw material having a hydroxyl group include hydroxyisophthalic acid.
聚醯胺樹脂例如可藉由包含單體(A-1)與單體(B-1) 的聚合性單體的縮合聚合而獲得。另外,亦可使用單體(A-1)的酯化物、醯鹵化物等代替單體(A-1)。聚合性單體亦可含有二異氰酸酯(單體(C-1))等其他單體。 Polyamine resin can be contained, for example, by including monomer (A-1) and monomer (B-1) Obtained by condensation polymerization of a polymerizable monomer. Further, an ester (A-1), a hydrazine halide or the like may be used instead of the monomer (A-1). The polymerizable monomer may also contain another monomer such as a diisocyanate (monomer (C-1)).
縮合聚合的方法並無特別限制,例如可採用如下方法:將聚合性單體溶解於溶劑中,在反應溫度0℃~200℃、反應時間1小時~10小時左右的條件下使之反應。 The method of the condensation polymerization is not particularly limited. For example, a method in which a polymerizable monomer is dissolved in a solvent and reacted at a reaction temperature of 0 ° C to 200 ° C and a reaction time of about 1 hour to 10 hours may be employed.
縮合聚合中所使用溶劑可列舉:N-甲基吡咯啶酮、N-乙基吡咯啶酮、N-甲基丁二醯亞胺、二甲基呋喃、甲苯、N,N'-二甲基乙醯胺、六亞甲基磷醯胺、二甲基亞碸等。其中,就樹脂的溶解性的觀點而言,較佳為N-甲基吡咯啶酮。 The solvent used in the condensation polymerization may, for example, be N-methylpyrrolidone, N-ethylpyrrolidone, N-methylbutylimine, dimethylfuran, toluene, N,N'-dimethyl Acetamide, hexamethylene phosphoniumamine, dimethyl alum, and the like. Among them, from the viewpoint of solubility of the resin, N-methylpyrrolidone is preferred.
另外,在縮合聚合中,以促進縮合反應為目的,可使用觸媒等加速劑。加速劑的添加量相對於聚合性單體10mol當量,較佳為設為0.1mol當量~50mol當量。加速劑可列舉:氯化鋰、氯化鈣、硫氰酸鈣(calcium rhodanide)等無機鹽,三乙基胺、吡啶等三級胺,四甲基氯化銨、四乙基溴化銨、四正丁基溴化銨等四級銨鹽等。 Further, in the condensation polymerization, an accelerator such as a catalyst may be used for the purpose of promoting the condensation reaction. The amount of the accelerator added is preferably from 0.1 mol equivalent to 50 mol equivalent based on 10 mol equivalents of the polymerizable monomer. Examples of the accelerator include inorganic salts such as lithium chloride, calcium chloride, and calcium rhodanide; tertiary amines such as triethylamine and pyridine; tetramethylammonium chloride and tetraethylammonium bromide; A quaternary ammonium salt such as tetra-n-butylammonium bromide or the like.
聚醯胺樹脂亦可為使利用縮合聚合獲得的聚合物進而改質而成的聚醯胺樹脂(改質聚醯胺樹脂),改質聚醯胺樹脂可列舉:烯烴改質聚醯胺、烷氧基矽烷改質聚醯胺、矽氧烷改質聚醯亞胺、環氧改質聚醯胺、聚碳酸酯改質聚醯胺、異氰酸酯改質聚醯胺等。 The polyamine resin may be a polyamine resin (modified polyamine resin) which is modified by a polymer obtained by condensation polymerization, and the modified polyamine resin may be exemplified by an olefin-modified polyamine. The alkoxydecane modified polyamine, the decane modified polyimine, the epoxy modified polyamine, the polycarbonate modified polyamine, the isocyanate modified polyamine, and the like.
(環氧樹脂) (epoxy resin)
就有效率地進行交聯的觀點而言,作為具有環氧基的化合物的環氧樹脂較佳為具有兩個以上的環氧基。具體例可例示:雙酚A型環氧樹脂、聯苯型環氧樹脂、萘型環氧樹脂、雙酚F型環氧樹脂、含磷環氧樹脂、雙酚S型環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚的二縮水甘油醚化物、萘二醇的二縮水甘油醚化物、酚類的二縮水甘油醚化物、醇類的二縮水甘油醚化物、以及該些的烷基取代物、鹵化物、氫化物等。該些環氧樹脂可單獨使用或組合使用兩種以上。 From the viewpoint of efficiently crosslinking, the epoxy resin as the epoxy group-containing compound preferably has two or more epoxy groups. Specific examples can be exemplified by bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus containing epoxy resin, bisphenol S type epoxy resin, and alicyclic ring. Epoxy resin, aliphatic chain epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, diglycidyl ether of bisphenol, naphthalene A diglycidyl ether compound of a diol, a diglycidyl ether compound of a phenol, a diglycidyl ether compound of an alcohol, and an alkyl substituent, a halide, a hydride, or the like. These epoxy resins may be used alone or in combination of two or more.
環氧樹脂亦可更含有環氧硬化劑。環氧硬化劑可列舉:苯酚型環氧硬化劑、甲酚型環氧硬化劑、酯型環氧硬化劑等。 The epoxy resin may also contain an epoxy hardener. Examples of the epoxy curing agent include a phenol type epoxy curing agent, a cresol type epoxy curing agent, and an ester type epoxy curing agent.
環氧樹脂的硬化促進劑亦可添加咪唑類。咪唑類可列舉:咪唑、2-甲基咪唑、2-十一烷基咪唑、1,2-二甲基咪唑、2-乙基-4-咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、2-苯基咪唑啉、萘并咪唑、吡唑、三唑、四唑、吲唑、吡啶、吡嗪、噠嗪、嘧啶、苯并三唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸鹽、1-氰基乙基-2-苯基咪唑鎓偏苯三酸鹽等。 An imidazole may also be added to the hardening accelerator of the epoxy resin. Examples of the imidazoles include imidazole, 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-imidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazoline, naphthoimidazole, pyrazole, triazole, tetrazole, oxazole, pyridine, pyrazine, Pyridazine, pyrimidine, benzotriazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Pyrimidine hydrazine trimellitate and the like.
黏著劑組成物中,相對於黏著劑組成物的固體成分量, 環氧樹脂相對於聚醯胺樹脂的添加量較佳為0.01質量%~50質量%,更佳為0.1質量%~30質量%,進而較佳為0.5質量%~20質量%,尤佳為1質量%~15質量%。若為該範圍,則可維持充分的耐化學品性,且作為黏著劑的功能提高。 In the adhesive composition, relative to the solid content of the adhesive composition, The amount of the epoxy resin added to the polyamide resin is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 30% by mass, still more preferably 0.5% by mass to 20% by mass, and particularly preferably 1%. Mass%~15% by mass. If it is this range, sufficient chemical resistance can be maintained and the function as an adhesive improves.
黏著劑組成物中的環氧樹脂以及聚醯胺樹脂的合計含量相對於黏著劑組成物總量,較佳為40質量%~100質量%,較佳為80質量%~100質量%,更佳為100質量%,即由環氧樹脂以及聚醯胺樹脂構成。 The total content of the epoxy resin and the polyamide resin in the adhesive composition is preferably 40% by mass to 100% by mass, preferably 80% by mass to 100% by mass, based on the total amount of the adhesive composition. It is 100% by mass, that is, it is composed of an epoxy resin and a polyamide resin.
就提高密接性的觀點而言,黏著劑組成物亦可於無損發明的目的之範圍內含有松香樹脂、萜烯樹脂、香豆酮(coumarone)樹脂、酚樹脂、苯乙烯樹脂、脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族芳香族共聚合系石油樹脂等黏著賦予劑等。 From the viewpoint of improving the adhesion, the adhesive composition may contain rosin resin, terpene resin, coumarone resin, phenol resin, styrene resin, aliphatic petroleum in the scope of the object of the invention. An adhesion-imparting agent such as a resin, an aromatic petroleum resin, or an aliphatic aromatic copolymer-based petroleum resin.
另外,黏著劑組成物亦可含有合金粒子、玻璃粒子、黏土粒子等無機材料,聚合物粒子等有機材料。更具體而言,合金粒子可列舉:錫合金、鉛合金、銦合金、鋅合金、金合金等,玻璃可列舉:鉛系、磷酸鹽系、硼酸系、釩酸鹽系、碲化物(telluride)系、氟化物系玻璃等,黏土可列舉:矽鎂石(stevensite)、蒙脫石(montmorillonite)、高嶺土(kaolinite)、伊利石(illite)、膨潤石(smectite)、綠泥石(chlorite)、蛭石(vermiculite)等,聚合物粒子可列舉:聚對苯二甲酸乙二酯、聚丙烯腈、氟樹脂(聚四氟乙烯(polytetrafluoroethylene,PTFE))、環氧樹脂、尼龍、聚醯亞胺、聚醯胺醯亞胺、聚萘二甲酸乙二酯等。 Further, the adhesive composition may contain an inorganic material such as alloy particles, glass particles or clay particles, or an organic material such as polymer particles. More specifically, examples of the alloy particles include a tin alloy, a lead alloy, an indium alloy, a zinc alloy, and a gold alloy. Examples of the glass include a lead system, a phosphate system, a boric acid system, a vanadate system, and a telluride. Fluoride-based glass, etc., examples of clay include: stevensite, montmorillonite, kaolinite, illite, smectite, chlorite, Vermiculite, etc., polymer particles include polyethylene terephthalate, polyacrylonitrile, fluororesin (polytetrafluoroethylene (PTFE)), epoxy resin, nylon, polyimine , polyamidoximine, polyethylene naphthalate, and the like.
黏著劑組成物較佳為不含胺、羧酸、酸酐、過氧化物等硬化觸媒,含有硬化觸媒的情況下的硬化觸媒的含量相對於黏著劑組成物的固體成分量,較佳為1質量%以下,更佳為0.5質量%以下。 The adhesive composition preferably contains no hardening catalyst such as an amine, a carboxylic acid, an acid anhydride or a peroxide, and the content of the hardening catalyst in the case of containing a hardening catalyst is preferably relative to the solid content of the adhesive composition. It is 1% by mass or less, more preferably 0.5% by mass or less.
黏著劑組成物亦可以膜狀提供。即,提供包含上述黏著劑組成物的膜狀黏著劑。膜狀黏著劑可設為包含單層或多層黏著劑組成物的層的膜狀黏著劑、或在支持體的單面或雙面形成有單層或多層黏著劑組成物的層的膜狀黏著劑。將膜狀黏著劑的製造方法的例子示於以下。 The adhesive composition can also be provided in the form of a film. That is, a film-like adhesive containing the above-described adhesive composition is provided. The film-like adhesive may be a film-like adhesive comprising a layer of a single-layer or multi-layered adhesive composition, or a film-like adhesive layer having a single-layer or multi-layered adhesive composition formed on one or both sides of the support. Agent. An example of a method for producing a film adhesive is shown below.
例如,可藉由將包含黏著劑組成物的黏著劑組成物清漆塗佈於支持體的一面上並使之乾燥,而製作膜狀黏著劑。 For example, a film-like adhesive can be produced by applying an adhesive composition varnish containing an adhesive composition onto one side of a support and drying it.
另外,可藉由將黏著劑組成物清漆塗佈於支持體的雙面上並使之乾燥,而製作在支持體的雙面具有黏著劑組成物的層的膜狀黏著劑。 Further, a film-like adhesive having a layer having an adhesive composition on both sides of the support can be produced by applying the adhesive composition varnish to both sides of the support and drying it.
進而,將藉由將黏著劑組成物清漆塗佈於脫模膜等膜上並使之乾燥而形成的黏著劑組成物的層積層(laminate)於支持體上而進行轉印,藉此亦可製作膜狀黏著劑。 Further, a layer of an adhesive composition formed by applying an adhesive composition varnish to a film such as a release film and drying it is transferred onto a support and transferred. Make a film adhesive.
此種利用澆鑄法(casting method)的製作方法就容易獲得平坦的黏著劑組成物的層而言較佳。 Such a method of using a casting method is preferable in that it is easy to obtain a layer of a flat adhesive composition.
黏著劑組成物的層的厚度較佳為0.1μm~100μm,更佳為1μm~50μm。黏著劑組成物的層的厚度可藉由黏著劑組成物清漆中的黏著劑組成物的濃度、以及黏著劑組成物清漆的塗佈量 而適當調整。 The thickness of the layer of the adhesive composition is preferably from 0.1 μm to 100 μm, more preferably from 1 μm to 50 μm. The thickness of the layer of the adhesive composition can be determined by the concentration of the adhesive composition in the adhesive composition varnish and the coating amount of the adhesive composition varnish. And adjust it appropriately.
黏著劑組成物清漆中所使用的溶劑並無特別限制,就黏著劑組成物顯示良好的溶解性而言,較佳為使用二醇系溶劑、二醇醚系溶劑、二醇酯系溶劑等。 The solvent used in the varnish of the adhesive composition is not particularly limited, and a diol solvent, a glycol ether solvent, a glycol ester solvent or the like is preferably used in terms of exhibiting good solubility of the adhesive composition.
具體而言,可列舉:乙二醇、二乙二醇、三乙二醇、丙二醇、乙二醇、二乙二醇、三乙二醇、丙二醇、二乙二醇單甲醚、三乙二醇單甲醚、丙二醇單甲醚、3-甲氧基-3-甲基-1-丁醇、乙二醇單甲醚乙酸酯、PMA(丙二醇單甲醚乙酸酯)、二乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯等。此外,亦可使用N-甲基吡咯啶酮、N-乙基吡咯啶酮、N-甲基丁二醯亞胺、N,N'-二甲基乙醯胺、二甲基甲醯胺等。該些溶劑可單獨使用或混合使用兩種以上。 Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, and triethylene glycol. Alcohol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene Alcohol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and the like. Further, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylbutylimine, N,N'-dimethylacetamide, dimethylformamide, etc. may also be used. . These solvents may be used alone or in combination of two or more.
支持體並無特別限制,較佳為使用具有對200℃以上的溫度的耐熱性的材料,可列舉包含聚酯、聚醯亞胺、聚醯胺、聚醚碸、聚苯硫醚、聚醚酮、聚醚醚酮、三乙醯纖維素、聚醚醯亞胺、聚萘二甲酸乙二酯、聚丙烯、丙烯酸、聚苯乙烯、聚碳酸酯等有機材料的材料。另外,亦可使用包含無機材料的支持體,可使用包含鋁、鎂、鈦、鉻、錳、鐵、鎳、鋅、錫、玻璃、矽晶圓(silicon wafer)、合金等無機材料的材料。 The support is not particularly limited, and a material having heat resistance to a temperature of 200 ° C or higher is preferably used, and examples thereof include polyester, polyimine, polyamine, polyether oxime, polyphenylene sulfide, and polyether. A material of an organic material such as a ketone, a polyetheretherketone, a triacetonitrile cellulose, a polyether quinone, a polyethylene naphthalate, a polypropylene, an acrylic acid, a polystyrene, or a polycarbonate. Further, a support containing an inorganic material may be used, and a material containing an inorganic material such as aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, silicon wafer, or alloy may be used.
本實施方式的黏著劑組成物可在室溫下黏附,在200℃~270℃下亦具有充分的接著性。本實施方式的黏著劑組成物的黏著力較佳為0.1N/cm~8.0N/cm,更佳為0.3N/cm~5.0N/cm,進而較佳為0.5N/cm~2.0N/cm。 The adhesive composition of the present embodiment can be adhered at room temperature and has sufficient adhesion at 200 ° C to 270 ° C. The adhesive force of the adhesive composition of the present embodiment is preferably from 0.1 N/cm to 8.0 N/cm, more preferably from 0.3 N/cm to 5.0 N/cm, still more preferably from 0.5 N/cm to 2.0 N/cm. .
可供黏著劑組成物接著的較佳的被黏接體較佳為具有對200℃以上的溫度的耐熱性的材料。更具體的被黏接體只要可達成本發明的目的,則並無特別限制,例如可列舉:尼龍6、尼龍66、尼龍46等聚醯胺樹脂,聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸丁二酯等聚酯樹脂,聚丙烯、聚乙烯等聚烯烴樹脂,丙烯酸系樹脂、聚醯亞胺樹脂、聚醚碸樹脂、聚苯硫醚樹脂、聚醚酮樹脂、聚醚醚酮樹脂、三乙醯纖維素樹脂、聚醚醯亞胺樹脂、聚碳酸酯樹脂、聚芳酯(polyallylate)樹脂或該些的混合樹脂,鋁、鎂、鈦、鉻、錳、鐵、鎳、鋅、錫、玻璃、銅、矽晶圓以及合金。該些材料之中,就顯示較高的耐熱性而言,更佳為聚酯樹脂、聚醯胺樹脂、聚烯烴樹脂、聚醯亞胺樹脂、丙烯酸系樹脂、鋁、鎂、鈦、鉻、錳、鐵、鎳、鋅、錫、玻璃、銅以及矽晶圓。 The preferred adherend for the adhesive composition is preferably a material having heat resistance to a temperature of 200 ° C or higher. The more specific adherend is not particularly limited as long as it can achieve the object of the invention, and examples thereof include polyamine resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate, and polynaphthalene. Polyester resin such as ethylene diformate, polytrimethylene terephthalate, poly(phthalic acid propylene dicarboxylate), polybutylene terephthalate or polybutylene naphthalate, polypropylene, polyethylene, etc. Polyolefin resin, acrylic resin, polyimide resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, polyether ether ketone resin, triacetyl cellulose resin, polyether oxime resin, Polycarbonate resin, polyallylate resin or a mixed resin thereof, aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, ruthenium wafer and alloy. Among these materials, in terms of exhibiting high heat resistance, a polyester resin, a polyamide resin, a polyolefin resin, a polyimide resin, an acrylic resin, aluminum, magnesium, titanium, chromium, or the like is more preferable. Manganese, iron, nickel, zinc, tin, glass, copper and tantalum wafers.
[實施例] [Examples]
(合成例1) (Synthesis Example 1)
於具備攪拌機、回流冷卻器、溫度計以及氮氣導入管的可分離式燒瓶(separable flask)中,使間苯二甲醯氯(isophthaloyl dichloride)529.3g、對苯二甲醯氯(terephthaloyl dichloride)75.7g、聚丙二醇二胺(JEFFAMINE(註冊商標)D-2000,HUNTSMAN公司製造)447.2g、1,4-雙(3-胺基丙基)哌嗪462.8g以及亞甲基環己基二胺(Wandamin HM(註冊商標),新日本理化公司製造)93.9 g於N-甲基吡咯啶酮7609g中,在冰浴冷卻下縮合聚合1小時,在室溫下縮合聚合2小時。反應結束後,在反應混合液中添加3倍量的水,將不溶成分分離以及乾燥,藉此獲得重量平均分子量為45000的聚醯胺樹脂。 In a separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 529.3 g of isophthaloyl dichloride and 75.7 g of terephthaloyl dichloride were used. , polypropylene glycol diamine (JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMAN) 447.2 g, 1,4-bis(3-aminopropyl)piperazine 462.8 g, and methylene cyclohexyldiamine (Wandamin HM) (registered trademark), manufactured by New Japan Physical and Chemical Corporation) 93.9 g was condensed and polymerized in 7609 g of N-methylpyrrolidone under ice-cooling for 1 hour, and condensed and polymerized at room temperature for 2 hours. After completion of the reaction, three times the amount of water was added to the reaction mixture, and the insoluble components were separated and dried, whereby a polyamide resin having a weight average molecular weight of 45,000 was obtained.
(合成例2) (Synthesis Example 2)
於具有攪拌機、回流冷卻器、溫度計以及氮氣導入管的可分離式燒瓶中,使間苯二甲酸55.7g、對苯二甲酸41.8g、5-羥基間苯二甲酸15.3g、聚丙二醇二胺(JEFFAMINE(註冊商標)D-2000,HUNTSMAN公司製造,聚丙二醇的重複單元數:33)122.0g、1,4-雙(3-胺基丙基)哌嗪97.7g、雙(4-胺基環己基)甲烷(Wandamin HM(註冊商標),新日本理化公司製造)12.8g以及鐵粉0.37g於N-甲基吡咯啶酮650g中,在200℃下一面去除副生的水一面縮合聚合10小時。反應結束後,進行冷卻,添加亞甲基二苯基二異氰酸酯30.5g,在160℃下反應3小時,藉此獲得重量平均分子量為40000的聚醯胺樹脂的NMP溶液。 In a separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 55.7 g of isophthalic acid, 41.8 g of terephthalic acid, 15.3 g of 5-hydroxyisophthalic acid, and polypropylene glycol diamine ( JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMAN, the number of repeating units of polypropylene glycol: 33) 122.0 g, 1,4-bis(3-aminopropyl)piperazine 97.7 g, bis(4-amino ring) Hexyl)methane (Wandamin HM (registered trademark), manufactured by Nippon Chemical and Chemical Co., Ltd.) 12.8 g and iron powder 0.37 g in N-methylpyrrolidone 650 g, condensation polymerization was carried out for 10 hours while removing by-product water at 200 ° C . After completion of the reaction, the mixture was cooled, and 30.5 g of methylene diphenyl diisocyanate was added thereto, and the mixture was reacted at 160 ° C for 3 hours to obtain a NMP solution of a polyamine resin having a weight average molecular weight of 40,000.
(實施例1) (Example 1)
將合成例1的聚醯胺樹脂20g與環氧樹脂(日本化藥製造,商品名:NC-3000H)0.5g溶解於二甲基乙醯胺32g中而獲得樹脂清漆。 20 g of the polyamide resin of Synthesis Example 1 and 0.5 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) were dissolved in 32 g of dimethylacetamide to obtain a resin varnish.
使用所獲得的樹脂清漆,利用棒式塗佈機(bar coater)以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET(聚對苯二甲酸乙二酯)膜上,並使用熱風乾燥機在160℃下乾燥 30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, the varnish was uniformly applied to a release PET (polyethylene terephthalate) film by a bar coater so that the thickness of the resin after drying became 20 μm. And dried at 160 ° C using a hot air dryer After 30 minutes, a film adhesive was formed.
(實施例2) (Example 2)
將合成例1的聚醯胺樹脂20g與環氧樹脂(日本化藥製造,商品名:NC-3000H)1.0g溶解於二甲基乙醯胺32g中而獲得樹脂清漆。 20 g of the polyamide resin of Synthesis Example 1 and 1.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) were dissolved in 32 g of dimethylacetamide to obtain a resin varnish.
使用所獲得的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.
(實施例3) (Example 3)
將合成例1的聚醯胺樹脂20g與環氧樹脂(日本化藥製造,商品名:NC-3000H)2.0g溶解於二甲基乙醯胺32g中而獲得樹脂清漆。 20 g of the polyamide resin of Synthesis Example 1 and 2.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) were dissolved in 32 g of dimethylacetamide to obtain a resin varnish.
使用所獲得的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.
(實施例4) (Example 4)
於包含合成例2的聚醯胺樹脂20g的NMP溶液中溶解環氧樹脂(日本化藥製造,商品名:NC-3000H)0.5g而獲得樹脂清漆。 A resin varnish was obtained by dissolving 0.5 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.
使用所獲得的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.
(實施例5) (Example 5)
於包含合成例2的聚醯胺樹脂20g的NMP溶液中溶解環氧樹脂(日本化藥製造,商品名:NC-3000H)1.0g而獲得樹脂清漆。 A resin varnish was obtained by dissolving 1.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.
使用所獲得的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.
(實施例6) (Example 6)
於包含合成例2的聚醯胺樹脂20g的NMP溶液中溶解環氧樹脂(日本化藥製造,商品名:NC-3000H)2.0g而獲得樹脂清漆。 A resin varnish was obtained by dissolving 2.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.
使用所獲得的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.
(實施例7) (Example 7)
於包含合成例2的聚醯胺樹脂20g的NMP溶液中溶解環氧樹脂(新日鐵住金化學製造,商品名:YDF-8170C)1.0g而獲得樹脂清漆。 A resin varnish was obtained by dissolving 1.0 g of an epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name: YDF-8170C) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.
使用所獲得的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.
(比較例1) (Comparative Example 1)
將合成例1的聚醯胺樹脂20g溶解於二甲基乙醯胺32g中而獲得樹脂清漆。 20 g of the polyamide resin of Synthesis Example 1 was dissolved in 32 g of dimethylacetamide to obtain a resin varnish.
使用所獲得的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚 度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the obtained resin varnish, using a bar coater to dry the resin thickness The varnish was uniformly applied to the release PET film in such a manner that the degree was 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer to form a film-like adhesive.
(比較例2) (Comparative Example 2)
使用合成例2的樹脂清漆,利用棒式塗佈機以乾燥後的樹脂厚度成為20μm的方式將清漆均勻地塗佈於脫模PET膜上,並使用熱風乾燥機在160℃下乾燥30分鐘,而形成膜狀黏著劑。 Using the resin varnish of Synthesis Example 2, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.
針對實施例1~實施例7以及比較例1、比較例2中所獲得的膜狀黏著劑,進行以下評價。將其結果示於表1。 The film adhesives obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were evaluated as follows. The results are shown in Table 1.
[耐化學品性評價] [Chemical resistance evaluation]
分別使用實施例1~實施例7以及比較例1、比較例2中所製作的膜狀黏著劑,向玻璃管瓶中添加膜(2cm見方)、及表1中所示的溶劑(10mL),利用攪拌轉子(mix rotor)在25℃下攪拌8小時。溶解試驗後,將膜取出,根據在160℃下乾燥30分鐘後的質量基準的殘膜率評價耐化學品性。 Using the film-like adhesives produced in Examples 1 to 7 and Comparative Examples 1 and 2, a film (2 cm square) and a solvent (10 mL) shown in Table 1 were added to the glass vial. The mixture was stirred at 25 ° C for 8 hours using a mixing rotor. After the dissolution test, the film was taken out, and the chemical resistance was evaluated based on the residual film ratio of the mass basis after drying at 160 ° C for 30 minutes.
[黏著力評價] [Adhesion evaluation]
將實施例1~實施例7以及比較例1、比較例2中所製作的膜狀黏著劑分別夾於聚醯亞胺膜(東麗杜邦(TORAY-DUPONT)製造,商品名:Kapton EN,厚度:25μm)與玻璃(日本電氣硝子製造,商品名:OA-10G)之間,利用手壓輥(hand roller)進行壓接,測定在200℃下加熱30分鐘後的黏著力。具體而言,將膜狀黏著劑的一端自玻璃板剝離,並固定於拉伸測定器的拉伸治具。將玻璃板壓抵於平台(stage),提拉膜狀黏著劑而將其自玻璃 板剝離,進行90°剝離試驗。藉由該測定而測定膜狀黏著劑的黏著力。 The film-like adhesives produced in Examples 1 to 7 and Comparative Examples 1 and 2 were respectively sandwiched between polyimine films (manufactured by TORAY-DUPONT, trade name: Kapton EN, thickness). 25 μm) and glass (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G) were pressure-bonded by a hand roller, and the adhesion after heating at 200 ° C for 30 minutes was measured. Specifically, one end of the film-like adhesive is peeled off from the glass plate and fixed to a tensile jig of a tensile tester. Press the glass plate against the stage, lift the film adhesive and bring it from the glass The plate was peeled off and subjected to a 90° peel test. The adhesion of the film adhesive was measured by this measurement.
[耐熱性評價] [Heat resistance evaluation]
針對黏著力評價中所製作的構造體,反覆進行三次如下操作:自室溫加熱至250℃,在該溫度下保持30分鐘以及在室溫下放置冷卻,觀察此時的外觀,並測定黏著力,對耐熱性進行評價。作為耐熱性的評價項目,耐熱黏著力是以黏著力變化率即將第三次操作後的黏著力除以第一次操作後的黏著力所得的值的百分率表示。 For the structure prepared in the adhesion evaluation, the following operations were repeated three times: heating from room temperature to 250 ° C, holding at this temperature for 30 minutes, and cooling at room temperature, observing the appearance at this time, and measuring the adhesion, The heat resistance was evaluated. As an evaluation item of heat resistance, the heat-resistant adhesive force is expressed as a percentage of a value obtained by dividing the adhesive force change rate by the adhesion force after the third operation by the adhesion force after the first operation.
NMP:N-甲基吡咯啶酮 NMP: N-methylpyrrolidone
THF:四氫呋喃 THF: tetrahydrofuran
TMAH:2.38%氫氧化四甲基銨水溶液 TMAH: 2.38% aqueous solution of tetramethylammonium hydroxide
此外,表中所謂「白化」,是指因藉由溶劑進行處理而使膜變白。 In addition, the term "whitening" in the table means that the film is whitened by treatment with a solvent.
可明確,根據將聚醯胺樹脂以及環氧樹脂以特定的比率組合而成的實施例1~實施例7的膜狀黏著劑,耐熱性得以維持且可提高耐化學品性。另外,可明確,根據使用具有羥基的聚醯胺樹脂的實施例4~實施例7的膜狀黏著劑,耐化學品性進一步提高。另外,如由黏著力的測定結果所明確般,根據實施例1~實施例7的膜狀黏著劑,均可剝離。 It is clear that the film-like adhesives of Examples 1 to 7 in which the polyamide resin and the epoxy resin are combined at a specific ratio can maintain heat resistance and improve chemical resistance. Further, it was confirmed that the chemical resistance of the film-like adhesives of Examples 4 to 7 using the polyamine resin having a hydroxyl group was further improved. Further, the film-like adhesives according to Examples 1 to 7 can be peeled off as determined by the measurement results of the adhesive force.
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-
2013
- 2013-10-11 JP JP2014540910A patent/JP6252483B2/en not_active Expired - Fee Related
- 2013-10-11 KR KR1020157009599A patent/KR20150070154A/en not_active Application Discontinuation
- 2013-10-11 TW TW102136809A patent/TW201418396A/en unknown
- 2013-10-11 WO PCT/JP2013/077790 patent/WO2014058058A1/en active Application Filing
- 2013-10-11 TW TW102136811A patent/TW201420709A/en unknown
- 2013-10-11 KR KR1020157009563A patent/KR20150071015A/en not_active Application Discontinuation
- 2013-10-11 JP JP2014540908A patent/JP6252482B2/en not_active Expired - Fee Related
- 2013-10-11 CN CN201380053352.7A patent/CN104718265A/en active Pending
- 2013-10-11 WO PCT/JP2013/077781 patent/WO2014058056A1/en active Application Filing
- 2013-10-11 CN CN201380053010.5A patent/CN104704072A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI631180B (en) * | 2014-07-02 | 2018-08-01 | 東洋油墨Sc控股股份有限公司 | Thermosetting resin composition, bonding sheet, cured product, and printed wiring board |
Also Published As
Publication number | Publication date |
---|---|
JP6252482B2 (en) | 2017-12-27 |
WO2014058058A1 (en) | 2014-04-17 |
TW201420709A (en) | 2014-06-01 |
JP6252483B2 (en) | 2017-12-27 |
JPWO2014058056A1 (en) | 2016-09-05 |
CN104704072A (en) | 2015-06-10 |
CN104718265A (en) | 2015-06-17 |
KR20150071015A (en) | 2015-06-25 |
KR20150070154A (en) | 2015-06-24 |
JPWO2014058058A1 (en) | 2016-09-05 |
WO2014058056A1 (en) | 2014-04-17 |
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